CA1060145A - Process for the polymerization of unsaturated compounds - Google Patents
Process for the polymerization of unsaturated compoundsInfo
- Publication number
- CA1060145A CA1060145A CA230,438A CA230438A CA1060145A CA 1060145 A CA1060145 A CA 1060145A CA 230438 A CA230438 A CA 230438A CA 1060145 A CA1060145 A CA 1060145A
- Authority
- CA
- Canada
- Prior art keywords
- reaction
- carried out
- hydride
- process according
- atoms
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerization Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The present invention relates to an improved process for the polymerization of compounds contalning at least one olefine insaturation by means of a catalyst system constituted by a transition metal compound and a hydride derivative of alumi-nium selected between a) oligomer N-alkyl-imioalanes constituted by a variety of four and for six atoms ring structures of the type and b) and aluminium hydride oligomer derivatives having the general formula:
(XAlNR)X(XYAl)y(NHR)y This process has a good catalytic activity, a great polymerization reproducibility and gives final polymers having constant and improved properties.
The present invention relates to an improved process for the polymerization of compounds contalning at least one olefine insaturation by means of a catalyst system constituted by a transition metal compound and a hydride derivative of alumi-nium selected between a) oligomer N-alkyl-imioalanes constituted by a variety of four and for six atoms ring structures of the type and b) and aluminium hydride oligomer derivatives having the general formula:
(XAlNR)X(XYAl)y(NHR)y This process has a good catalytic activity, a great polymerization reproducibility and gives final polymers having constant and improved properties.
Description
6~
The pre~ent i~sntion relates to an i..mproved proce~
for the polymerization of compound3 co.ntaining at l~ast one ole~
fine unsaturation by mean~ o~ a catalyst consistiny of a transition `~
metal compound and a cocatalyst consisting of a hyd~ide deEivative of aluminium selected between a) oligomer N-alkyl-iminoalanes haviDg th~ g~neral ~ormula -(Al~-NR)-n in which R represe.nts an aliphatic, cyclo~
aliphatic or aromatic hydrocarbon radical and n i5 an integer lower than or equal to 10, which N-alkyl-imiDoalane~ are con5ti~
tuted by a variety of condeDsed four and/or six atoms ri~g ~ructures of the type - HAl - R - / NR ;.
- RN - H- _ HAl AlH _ (I) ..
- RN NR
AlH . .
wherei~ the rings have unities (HAl-NR) in common,wi~h or without .
partial ~ubstitution o~ hydride hydrogen atoms by haloge.n atoms, and.
b) oligomer derivatives having the following general ` ~ , .: . . .
. formula .
(X Al NR)X (X Y Al)y (~)y (II) in which R represerts an aliphatic, aromatic, cycloaliphatic hydrocarbo~ radical, X and Y are ~ame or dif~erent and each repre~ent a hydridb hydroge~ and/or a haloge~ atom directly bond ; ~o al1~m~nium, the halogen atom number being lower than ~ ~ 2y .. ~ -: ` and the difference therefrom being co.~tituted b~ hydride hydroge~
atoms; and the ~um x ~ g i3 an i.nteger lower t~a~ or equal to 10~ .
~ being a~ i~tegex other than zero~
'',, ~:
`'3 , ,:
The term "hydride hydroc~ens" refers to hydrogen atoms directly bonded to aluminium, which can be analytically determined ~ :
according to known methods.
In the aforesaid formula (II), x and y do not necessa-rily refer to repea-ted imine or amine unities having the same composition, based on the meanings of X and Y.
The compounds of the formula (I) form the subject . matter of a c~pending Canadian application serial no. 230,579 filed July 2, 1975. They have a tridimensional structure in the : Active H
: 10 form of a "cage" and show Al atomic ratios equal or substantially equal to 1 and N/Al ra-tios equal to 1.
The compounds of the formula (II) form the subject .`
matter of another copending Canadian application serial no.
; 230,436 filed June 30, 1975. They have the following atomic . ratios: N/Al_ 1, (X~Y)/Al ?1.
According to a preferred embodiment of the invention .. ~ the compounds having the formula (II) are ring condensed, mono~
: or polycyclic oligomer derivatives containing aluminium.and . nitrogen atoms. For instance, they are four and/or six atoms . . .
. 20 ring derivatives, exemplified by the formula I', II' and III' . / AlH \ / AlH2 RH~ - AlH -HR N NR - -RN NR - ` XHAl NR -: ~IAl AlH- -HAl AlH-: \ / \ / , NR NHR
~ wherein the residual valences are partially or totally saturated .
; by hydrogen or halogen atoms and/or are condensated with other : rings of the same type or of the type IV' and V' ." .'~ ~.
.: ~
.. ... _ .. . . ..
~ , - 2 '~
106~45 ~ ~
AlH :`
HAl AlH~ lEI-I R
( IV) ' ( ~
.: - `
~ he ge~er~l formula (II) refers c~so to co~pou~ds haning tridimensional structures in the ~orm of "open cage", resultiDg from the conde~atio~ of the abovesaid rings with imln~ unities and/or with 4 and/or 6 atoms open rings of the type, for i.nstance H2~1 - NHR .NR
t I I / \ `; ;:
-RN - AlHX RHN - AlHX ~1 AlHX
RN NHR
, \ /
(IV) ' (VII) The aforesaid general formula re~ers also to:composi~
tions wherein the groups AlXY and ~HR are in immediate vici~ity or are separated ol~e from the other i:n the moleoule so that no ~: .
..:
.:; interactioD occur~ without a substc~tial structurc~l rearrangement.
~he i.nventive polymerization is based o~ the use o~
high purity co-catalyst~, which give rise to better and more .
reproducible complexation, exchange, reduction reactions with`:
transition metal compounds. Inter alia, the reactio.n by-products, that are ~ot direotly i~volved in forming the cataly~b centres, have predetermired physical-Chemical propertle3 (for e~ample, solubility3, and th$re~or it is po~sible to control and/or to .~ avoid unwished sec~ndary reactions such a~ cyclization9 cross- ~.
. liDking, chain-transfer, isomerization9 etc~ ..
~he inve~tive process is chaxacterized by a good cata-3 Iytic activity joined to a greater polymerization reproducibili-ty and to improved and more constant properties of the ~i~al :polymer~
~ 3 ~
` ~ ~ 6~ ~ ~ 5 The invent~ve polymerizatio~ reactio~ ls carried out :~
at temperatuxes ranging ~rom -78 to +150C, under pre~ure~ rangi~g from the room o~e to 15d atmosphere~. ~he operation~ are graduall~
performed in the pre~ence of a solvent ine:rt to the catalyst, pre-~erably selected among aliphatic, aromatic, cycloaliphatic hydro~ :
carbo.ns. ;
Depend~ng UpOD the mo~omer to be polymerized, the yield sf ~olid polymer ~nd the phy~ical-chemical, mechanical, dyn~mi¢, `~`
etc., properties thereof are affected by the cocataly~t/catalyst :
molar ratio, expres~ed as hydride hydrogen/transition me~al atomic :~
ratio, this rat~o bei~g pre~rably equal to or highex tha~ 1. -~he catalyst-cocatal~st interaction may be realized . :~
either in the presence or in th0 ab~nce o~ the mo~omer to be . polymerized. I~ the latter ca~e9 the r~actio~ mi~ture m~y be "
allowed to ~tand for a give~ period at a temperatuxe e~ual to or different from the polymerizatio~ o~e.
XAMPIæ
:By operati:l~g u~der nitrogen atmosphere, 90 ml OI hexa~e7 ` 0.64 mmole of ~iC14 a~d (EAl-N-C3H6)6 iD a~amoullt equivalent to ~.:
0O93 m atoms of Al were introduced ~nto a bottle ~vi~g a 200 ml .~ ¢apacity. . I
~rdrogen developed a~d a brown precipltate was ~ormed.
~e reactlo~ mlxture was aged at room temperature for 10 minute~, the.n 20 g of isopreIle were ad~ed therei~.
~he bottle was sealed by a :~eo~r~ne crow~-closed plug :~
, . . .
a:~d put on a rotati:~g ca~rier l:n a bath ~e:rmos~ated at 30C. ~;
q~his temperature was kept for ~ro hours, then the ~ bottle wa~ open a~d the co:ntent wa~ poured into 800 ml of methyl ~ ai¢ohol to which an antio~ldant was prealabl~ added. ~he coagu-. . .
lated white pol~mer, having a~ elastio st~ucture, was ~ied under ~acuum at 50C for 20 hours. 8~3 g of a solid polg~er wer~
oW ai~ed having the following e~Ghai~emen~ o~ the isopre~e .. . . . .
~L060~5 ~- ~
monomer unitie~:
1,4 cis % = 96,8 174 trans % - O 1,2 9~ - O
3,4 % = 3,2 total un~atuxations ~ 96~90 /~ ~ in toluene at 30C was 6.29 dl/g~ ;
~XAMP$E 2 Under the ~ame operat~ve co~ditions ~ example 1, isopre~e was polymerized by u~ing a mixture containing (~
C4Hg)6 and ~iC14 and having the ~ollowi~g compositio~:
- hexane - 90 ml ,~ ~
lo - Tial4 ~ 0,64 mmole ~ .
; - (HAl-~-C4Hg)6 = an amount equi~ale~t to 0.8 m, atoms ~.
Of Al : When the reaotion was achieved, 6.5 g o~ dry elastic po~ymer were obtained i~ which the monomer unity e~chai~ement wa~ :
. 1,4 bis % = g6.5 1,4 trans % = 0 1,2 % =
3,4 % = 3.5 total u~saturation = 93.6.
~ n toluene at 30C, was 4.69 dl/g.
E~XAMPIæ 3 U~der the same operative conditions o~ example ~, ~soprene wa~ polymerize~ bg employing a mixture containing (HAl-N-C4Hg)4 and ~iCl4, and having the following composltion:
- hexane a ~0 ml - ~iC14 = 0,64 mmole _ (~Al-~-C4Hg)4 = an amount equivale~t to 0.8~ m. atoms ~ :
Wh~n the reactio~ was completed, 8.7 g of dry ela~tic pol~mer were obtai~ed havi~g the following enchai~eme~t o~ ~he mcnomer unitie~:
1,4 ci~ = ~6.7 % 1,4 tra~s = O % 1,2 -3,4 = 3.3% ; total un~aturatlon _ 105 ; L-~ in toluene at 30C wa~ 3~6. ~.
,, :
1~160145 ` ~
~ ~ ,i .
~ I
Ui~der the ~ame operati~e co~ditio:~s o:l~ example 19 i~o~
pre~e was polymerized by using a mixture co~ta~ni~g (HAl-N-C4Hg) a~d ~iCl4 havi~g the rollowing composition~
- h~xa~e = 90 ml _ ~iC14 = 0964 mmole N-C4Hg)4 in ~ amount equal to û.93 :m atom of alumi~ium.
7.9 g of dry ela~tic polymer were obtail~ed ~ g the mo:nomer u:nity enchaineme:nt: ~ `
1,4 cis - 97.2 %; 1,4 trans = O %; 1,2 = O %;
3,4 - 208%; total unsaturatio~s = 111, r~ 7 at ~6C iD toluene, was 4.9.
E~AM~E~ ~ :
U~der the same operati~e collditions of example 1, i~opre~e was pol~merized b~ employing a mixture containing N~C4Eg)3 (ClLL-N-C4Hg)1 and ~lC14 havi~g ~he following composition:
- he~ane = 90 ml : - ~iC14 c 0.64 mmole .
20 ~ N-a4Hg)~ (ClAl-N-C4Hg~ in an amount corraspo~ding to 1.025 aluminium m. atoms~
7.8 g o~ dry elasti¢ polymer ware obtained having the followi~e enchainement of the monom~r unities: :
1,4 ci~ - 96.6 ~; 1,4 trans = O %; 1,2 , 0.1 %;
3,4 = ~.~ %; total u~saturation = 96.2. .
3 in tolu~ne at 30C was 5.68. :~
..
~j . ' ,. ' ~ - 6 -, ~ -. . .
The pre~ent i~sntion relates to an i..mproved proce~
for the polymerization of compound3 co.ntaining at l~ast one ole~
fine unsaturation by mean~ o~ a catalyst consistiny of a transition `~
metal compound and a cocatalyst consisting of a hyd~ide deEivative of aluminium selected between a) oligomer N-alkyl-iminoalanes haviDg th~ g~neral ~ormula -(Al~-NR)-n in which R represe.nts an aliphatic, cyclo~
aliphatic or aromatic hydrocarbon radical and n i5 an integer lower than or equal to 10, which N-alkyl-imiDoalane~ are con5ti~
tuted by a variety of condeDsed four and/or six atoms ri~g ~ructures of the type - HAl - R - / NR ;.
- RN - H- _ HAl AlH _ (I) ..
- RN NR
AlH . .
wherei~ the rings have unities (HAl-NR) in common,wi~h or without .
partial ~ubstitution o~ hydride hydrogen atoms by haloge.n atoms, and.
b) oligomer derivatives having the following general ` ~ , .: . . .
. formula .
(X Al NR)X (X Y Al)y (~)y (II) in which R represerts an aliphatic, aromatic, cycloaliphatic hydrocarbo~ radical, X and Y are ~ame or dif~erent and each repre~ent a hydridb hydroge~ and/or a haloge~ atom directly bond ; ~o al1~m~nium, the halogen atom number being lower than ~ ~ 2y .. ~ -: ` and the difference therefrom being co.~tituted b~ hydride hydroge~
atoms; and the ~um x ~ g i3 an i.nteger lower t~a~ or equal to 10~ .
~ being a~ i~tegex other than zero~
'',, ~:
`'3 , ,:
The term "hydride hydroc~ens" refers to hydrogen atoms directly bonded to aluminium, which can be analytically determined ~ :
according to known methods.
In the aforesaid formula (II), x and y do not necessa-rily refer to repea-ted imine or amine unities having the same composition, based on the meanings of X and Y.
The compounds of the formula (I) form the subject . matter of a c~pending Canadian application serial no. 230,579 filed July 2, 1975. They have a tridimensional structure in the : Active H
: 10 form of a "cage" and show Al atomic ratios equal or substantially equal to 1 and N/Al ra-tios equal to 1.
The compounds of the formula (II) form the subject .`
matter of another copending Canadian application serial no.
; 230,436 filed June 30, 1975. They have the following atomic . ratios: N/Al_ 1, (X~Y)/Al ?1.
According to a preferred embodiment of the invention .. ~ the compounds having the formula (II) are ring condensed, mono~
: or polycyclic oligomer derivatives containing aluminium.and . nitrogen atoms. For instance, they are four and/or six atoms . . .
. 20 ring derivatives, exemplified by the formula I', II' and III' . / AlH \ / AlH2 RH~ - AlH -HR N NR - -RN NR - ` XHAl NR -: ~IAl AlH- -HAl AlH-: \ / \ / , NR NHR
~ wherein the residual valences are partially or totally saturated .
; by hydrogen or halogen atoms and/or are condensated with other : rings of the same type or of the type IV' and V' ." .'~ ~.
.: ~
.. ... _ .. . . ..
~ , - 2 '~
106~45 ~ ~
AlH :`
HAl AlH~ lEI-I R
( IV) ' ( ~
.: - `
~ he ge~er~l formula (II) refers c~so to co~pou~ds haning tridimensional structures in the ~orm of "open cage", resultiDg from the conde~atio~ of the abovesaid rings with imln~ unities and/or with 4 and/or 6 atoms open rings of the type, for i.nstance H2~1 - NHR .NR
t I I / \ `; ;:
-RN - AlHX RHN - AlHX ~1 AlHX
RN NHR
, \ /
(IV) ' (VII) The aforesaid general formula re~ers also to:composi~
tions wherein the groups AlXY and ~HR are in immediate vici~ity or are separated ol~e from the other i:n the moleoule so that no ~: .
..:
.:; interactioD occur~ without a substc~tial structurc~l rearrangement.
~he i.nventive polymerization is based o~ the use o~
high purity co-catalyst~, which give rise to better and more .
reproducible complexation, exchange, reduction reactions with`:
transition metal compounds. Inter alia, the reactio.n by-products, that are ~ot direotly i~volved in forming the cataly~b centres, have predetermired physical-Chemical propertle3 (for e~ample, solubility3, and th$re~or it is po~sible to control and/or to .~ avoid unwished sec~ndary reactions such a~ cyclization9 cross- ~.
. liDking, chain-transfer, isomerization9 etc~ ..
~he inve~tive process is chaxacterized by a good cata-3 Iytic activity joined to a greater polymerization reproducibili-ty and to improved and more constant properties of the ~i~al :polymer~
~ 3 ~
` ~ ~ 6~ ~ ~ 5 The invent~ve polymerizatio~ reactio~ ls carried out :~
at temperatuxes ranging ~rom -78 to +150C, under pre~ure~ rangi~g from the room o~e to 15d atmosphere~. ~he operation~ are graduall~
performed in the pre~ence of a solvent ine:rt to the catalyst, pre-~erably selected among aliphatic, aromatic, cycloaliphatic hydro~ :
carbo.ns. ;
Depend~ng UpOD the mo~omer to be polymerized, the yield sf ~olid polymer ~nd the phy~ical-chemical, mechanical, dyn~mi¢, `~`
etc., properties thereof are affected by the cocataly~t/catalyst :
molar ratio, expres~ed as hydride hydrogen/transition me~al atomic :~
ratio, this rat~o bei~g pre~rably equal to or highex tha~ 1. -~he catalyst-cocatal~st interaction may be realized . :~
either in the presence or in th0 ab~nce o~ the mo~omer to be . polymerized. I~ the latter ca~e9 the r~actio~ mi~ture m~y be "
allowed to ~tand for a give~ period at a temperatuxe e~ual to or different from the polymerizatio~ o~e.
XAMPIæ
:By operati:l~g u~der nitrogen atmosphere, 90 ml OI hexa~e7 ` 0.64 mmole of ~iC14 a~d (EAl-N-C3H6)6 iD a~amoullt equivalent to ~.:
0O93 m atoms of Al were introduced ~nto a bottle ~vi~g a 200 ml .~ ¢apacity. . I
~rdrogen developed a~d a brown precipltate was ~ormed.
~e reactlo~ mlxture was aged at room temperature for 10 minute~, the.n 20 g of isopreIle were ad~ed therei~.
~he bottle was sealed by a :~eo~r~ne crow~-closed plug :~
, . . .
a:~d put on a rotati:~g ca~rier l:n a bath ~e:rmos~ated at 30C. ~;
q~his temperature was kept for ~ro hours, then the ~ bottle wa~ open a~d the co:ntent wa~ poured into 800 ml of methyl ~ ai¢ohol to which an antio~ldant was prealabl~ added. ~he coagu-. . .
lated white pol~mer, having a~ elastio st~ucture, was ~ied under ~acuum at 50C for 20 hours. 8~3 g of a solid polg~er wer~
oW ai~ed having the following e~Ghai~emen~ o~ the isopre~e .. . . . .
~L060~5 ~- ~
monomer unitie~:
1,4 cis % = 96,8 174 trans % - O 1,2 9~ - O
3,4 % = 3,2 total un~atuxations ~ 96~90 /~ ~ in toluene at 30C was 6.29 dl/g~ ;
~XAMP$E 2 Under the ~ame operat~ve co~ditions ~ example 1, isopre~e was polymerized by u~ing a mixture containing (~
C4Hg)6 and ~iC14 and having the ~ollowi~g compositio~:
- hexane - 90 ml ,~ ~
lo - Tial4 ~ 0,64 mmole ~ .
; - (HAl-~-C4Hg)6 = an amount equi~ale~t to 0.8 m, atoms ~.
Of Al : When the reaotion was achieved, 6.5 g o~ dry elastic po~ymer were obtained i~ which the monomer unity e~chai~ement wa~ :
. 1,4 bis % = g6.5 1,4 trans % = 0 1,2 % =
3,4 % = 3.5 total u~saturation = 93.6.
~ n toluene at 30C, was 4.69 dl/g.
E~XAMPIæ 3 U~der the same operative conditions o~ example ~, ~soprene wa~ polymerize~ bg employing a mixture containing (HAl-N-C4Hg)4 and ~iCl4, and having the following composltion:
- hexane a ~0 ml - ~iC14 = 0,64 mmole _ (~Al-~-C4Hg)4 = an amount equivale~t to 0.8~ m. atoms ~ :
Wh~n the reactio~ was completed, 8.7 g of dry ela~tic pol~mer were obtai~ed havi~g the following enchai~eme~t o~ ~he mcnomer unitie~:
1,4 ci~ = ~6.7 % 1,4 tra~s = O % 1,2 -3,4 = 3.3% ; total un~aturatlon _ 105 ; L-~ in toluene at 30C wa~ 3~6. ~.
,, :
1~160145 ` ~
~ ~ ,i .
~ I
Ui~der the ~ame operati~e co~ditio:~s o:l~ example 19 i~o~
pre~e was polymerized by using a mixture co~ta~ni~g (HAl-N-C4Hg) a~d ~iCl4 havi~g the rollowing composition~
- h~xa~e = 90 ml _ ~iC14 = 0964 mmole N-C4Hg)4 in ~ amount equal to û.93 :m atom of alumi~ium.
7.9 g of dry ela~tic polymer were obtail~ed ~ g the mo:nomer u:nity enchaineme:nt: ~ `
1,4 cis - 97.2 %; 1,4 trans = O %; 1,2 = O %;
3,4 - 208%; total unsaturatio~s = 111, r~ 7 at ~6C iD toluene, was 4.9.
E~AM~E~ ~ :
U~der the same operati~e collditions of example 1, i~opre~e was pol~merized b~ employing a mixture containing N~C4Eg)3 (ClLL-N-C4Hg)1 and ~lC14 havi~g ~he following composition:
- he~ane = 90 ml : - ~iC14 c 0.64 mmole .
20 ~ N-a4Hg)~ (ClAl-N-C4Hg~ in an amount corraspo~ding to 1.025 aluminium m. atoms~
7.8 g o~ dry elasti¢ polymer ware obtained having the followi~e enchainement of the monom~r unities: :
1,4 ci~ - 96.6 ~; 1,4 trans = O %; 1,2 , 0.1 %;
3,4 = ~.~ %; total u~saturation = 96.2. .
3 in tolu~ne at 30C was 5.68. :~
..
~j . ' ,. ' ~ - 6 -, ~ -. . .
Claims (5)
1 Process for the polymerization of compounds con-taining at least an olefine unsaturation characterized in that the reaction is carried out in the presence of a catalyst consist-ing of a transition metal compound, and a cocatalyst consisting of an aluminium hydride derivatives selected between a) oligomer N-alkyliminoalanes constituted by a variety of four and/or six atoms ring structures of the type in which R represents an aliphatic, cycloaliphatlc or aromatic hydrocarbon radical, which structures are joined altogether to give high purity tridimensional structures in the form of a cage, having the composition (HAl-NR)n in which R has the above-said meanings, n is an integer lower than or equal to 10, hydride hydrogens being partially or not substituted by halogen atoms;
and b) aluminium hydride oligomer derivatives having the general formula (XAlNR)x(XYAl)y(NHR)y in which R represents an aliphatic, cycloaliphatic, aromatic hydrocarbon radical; X and Y are same or different and each repre-sent a hydride hydrogen and/or a halogen atom directly bonded to aluminium, the number of halogen atoms being lower than x + 2y and the difference therefrom being constituted by hydride hydrogen atoms; the sum x + y is an integer lower than or equal to 10, y being an integer other than zero; provided that x and y do not necessarily refer to repeated imine or amine unities having the same composition, based on the meanings of X and Y.
and b) aluminium hydride oligomer derivatives having the general formula (XAlNR)x(XYAl)y(NHR)y in which R represents an aliphatic, cycloaliphatic, aromatic hydrocarbon radical; X and Y are same or different and each repre-sent a hydride hydrogen and/or a halogen atom directly bonded to aluminium, the number of halogen atoms being lower than x + 2y and the difference therefrom being constituted by hydride hydrogen atoms; the sum x + y is an integer lower than or equal to 10, y being an integer other than zero; provided that x and y do not necessarily refer to repeated imine or amine unities having the same composition, based on the meanings of X and Y.
2. Process according to claim 1, characterized in that the reaction is carried out at a cocatalyst/catalyst molar ratio equal to or higher than 1.
3. Process according to claim 1 or 2 9 characterized in that the reaction is carried out at temperatures ranging from -78 to 150°C.
4. Process according to claim 1 or 2, characterized in that the reaction is carried out under pressures ranging from the room pressure to 150 atmospheres.
5, Process according to claim 1 or 2, characterized in that the reaction is carried out in the presence of a solvent selected among the aliphatic, aromatic or cycloaliphatic hydro-carbons.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24659/74A IT1015581B (en) | 1974-07-01 | 1974-07-01 | PROCESS FOR THE POLYMERIZATION OF UNSATURATED COMPOUNDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1060145A true CA1060145A (en) | 1979-08-07 |
Family
ID=11214286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA230,438A Expired CA1060145A (en) | 1974-07-01 | 1975-06-30 | Process for the polymerization of unsaturated compounds |
Country Status (20)
| Country | Link |
|---|---|
| US (1) | US4032703A (en) |
| JP (1) | JPS5634007B2 (en) |
| BE (1) | BE830810A (en) |
| CA (1) | CA1060145A (en) |
| CH (1) | CH606137A5 (en) |
| CS (1) | CS183807B2 (en) |
| DD (1) | DD118656A5 (en) |
| DE (1) | DE2529299A1 (en) |
| DK (1) | DK147199C (en) |
| FR (1) | FR2277104A1 (en) |
| GB (2) | GB1508049A (en) |
| HU (1) | HU173518B (en) |
| IL (1) | IL47771A (en) |
| IT (1) | IT1015581B (en) |
| LU (1) | LU72854A1 (en) |
| NL (1) | NL177022C (en) |
| NO (1) | NO147424C (en) |
| SE (1) | SE426396B (en) |
| YU (1) | YU36982B (en) |
| ZA (1) | ZA754105B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59222774A (en) * | 1983-06-02 | 1984-12-14 | Shin Nippon Denko Kk | Testing apparatus for light emitting element |
| JPS61105473A (en) * | 1984-10-29 | 1986-05-23 | Daito Denshi Kogyo Kk | Inspecting device of laser diode |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL274340A (en) * | 1961-02-04 | |||
| NL130130C (en) * | 1961-07-17 | |||
| NL129055C (en) * | 1965-02-03 | 1900-01-01 | ||
| NL129054C (en) * | 1965-02-03 | |||
| JPS4321312Y1 (en) * | 1965-10-30 | 1968-09-07 | ||
| DE2110195C3 (en) * | 1970-03-11 | 1975-07-31 | Snam Progetti S.P.A., Mailand (Italien) | Aluminum compound, process for their preparation and their use in the polymerization of olefins, conjugated or non-conjugated dienes or mixtures thereof |
-
1974
- 1974-07-01 IT IT24659/74A patent/IT1015581B/en active
-
1975
- 1975-04-26 CS CS7500004544A patent/CS183807B2/en unknown
- 1975-06-19 GB GB14441/76A patent/GB1508049A/en not_active Expired
- 1975-06-19 GB GB26196/75A patent/GB1508044A/en not_active Expired
- 1975-06-25 NO NO752288A patent/NO147424C/en unknown
- 1975-06-26 ZA ZA00754105A patent/ZA754105B/en unknown
- 1975-06-26 YU YU1647/75A patent/YU36982B/en unknown
- 1975-06-26 CH CH831375A patent/CH606137A5/xx not_active IP Right Cessation
- 1975-06-26 FR FR7520157A patent/FR2277104A1/en active Granted
- 1975-06-30 BE BE157819A patent/BE830810A/en not_active IP Right Cessation
- 1975-06-30 HU HU75SA2810A patent/HU173518B/en unknown
- 1975-06-30 JP JP8014775A patent/JPS5634007B2/ja not_active Expired
- 1975-06-30 CA CA230,438A patent/CA1060145A/en not_active Expired
- 1975-06-30 DK DK295975A patent/DK147199C/en not_active IP Right Cessation
- 1975-06-30 LU LU72854A patent/LU72854A1/xx unknown
- 1975-07-01 SE SE7507561A patent/SE426396B/en not_active IP Right Cessation
- 1975-07-01 US US05/592,249 patent/US4032703A/en not_active Expired - Lifetime
- 1975-07-01 DD DD187008A patent/DD118656A5/xx unknown
- 1975-07-01 NL NLAANVRAGE7507844,A patent/NL177022C/en not_active IP Right Cessation
- 1975-07-01 DE DE19752529299 patent/DE2529299A1/en active Pending
- 1975-07-23 IL IL47771A patent/IL47771A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GB1508049A (en) | 1978-04-19 |
| DK147199C (en) | 1984-11-19 |
| NO752288L (en) | 1976-01-05 |
| NL7507844A (en) | 1976-01-05 |
| CH606137A5 (en) | 1978-10-31 |
| FR2277104B1 (en) | 1980-04-30 |
| NO147424B (en) | 1982-12-27 |
| JPS5634007B2 (en) | 1981-08-07 |
| LU72854A1 (en) | 1975-10-08 |
| IL47771A (en) | 1979-01-31 |
| YU164775A (en) | 1982-02-25 |
| CS183807B2 (en) | 1978-07-31 |
| NL177022B (en) | 1985-02-18 |
| GB1508044A (en) | 1978-04-19 |
| NO147424C (en) | 1983-04-06 |
| IL47771A0 (en) | 1975-10-15 |
| NL177022C (en) | 1985-07-16 |
| JPS5128190A (en) | 1976-03-09 |
| IT1015581B (en) | 1977-05-20 |
| HU173518B (en) | 1979-06-28 |
| DK147199B (en) | 1984-05-14 |
| DD118656A5 (en) | 1976-03-12 |
| DK295975A (en) | 1976-01-02 |
| SE7507561L (en) | 1976-01-02 |
| DE2529299A1 (en) | 1976-01-15 |
| BE830810A (en) | 1975-10-16 |
| US4032703A (en) | 1977-06-28 |
| YU36982B (en) | 1984-08-31 |
| FR2277104A1 (en) | 1976-01-30 |
| AU8212175A (en) | 1976-12-16 |
| ZA754105B (en) | 1976-06-30 |
| SE426396B (en) | 1983-01-17 |
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